TW201004893A - Oxide sintered object, sputtering target comprising the sintered object, process for producing the sintered object, and process for producing sputtering target comprising the sintered object - Google Patents

Abstract

An oxide sintered object which comprises a composite oxide of lanthanum and hafnium, characterized in that the amount of the hafnium contained in the sintered object is equivalent to or larger than that of the lanthanum. A process for producing a sintered object of an oxide of lanthanum and hafnium is provided which is characterized by using an La2(CO3)3 powder and an HfO2 powder as raw-material powders, mixing the powders so that the Hf/La molar ratio becomes 1-1.2, thereafter heating the powder mixture in the air to conduct synthesis, subsequently pulverizing the synthesized material into a powder, and then hot-pressing the synthesis powder to form a sintered object. Lanthanum metal combines rapidly with oxygen and disintegrates, while lanthanum oxide combines with water to form the hydroxide and changes to a powder. Both lanthanum metal and lanthanum oxide have hence had a problem that long-term storage is difficult and a sputtering target, even when produced, cannot be actually used. In view of this, the stable lanthanum-containing oxide sintered object comprising an oxide of lanthanum (La) and hafnium (Hf) is provided. A lanthanum-containing oxide sputtering target especially suitable for use in forming a high-k gate insulating film is provided.

Description

201004893 VI. INSTRUCTION DESCRIPTION OF THE INVENTION [Technical Field] The present invention relates to an oxide sintered body composed of oxides of lanthanum (La) and hafnium (Hf), and sputtering by the sintered body A method for producing a target, a structure, and a method for producing the sintered body sputtering target. [Prior Art] Recently, the next generation MOSFET (Metal-Oxide-Semiconduct〇r

Field Effect Transistor, Metal Oxide Semiconductor Field Effect Transistor) The gate insulating film in germanium is required to be thinned, but in the Si〇2 used as a gate insulating film, the leakage current due to tunneling is increased. Therefore, normal operation becomes difficult. Therefore, as an alternative material, high-k dielectric constants, high thermal stability, and Hf〇2, Zr〇2, Al2〇3, La203, etc., which have high energy barriers to holes and electrons in the crucible, are proposed. (high dielectric constant) material. Among the materials that are favored, Hf〇2 is the basic material system, and a research report on the gate insulating film in the next generation MOSFET is proposed. In the vicinity of ®, it has been found that by using a high-k material of Hf lanthanum in combination with oxidized ruthenium (仏〇3), it is possible to obtain an improvement in characteristics such as reduction of a threshold voltage, and it has been widely recognized as an electronic material. Lanthanum (La) is contained in the rare earth element and is contained in the earth's crust as a mineral resource with a mixed oxide. The rare earth elements are relatively rare. The minerals are separated from each other, so this name is obtained, but the whole crust is not rare. The atomic number of the program is 57, which is a white metal with an atomic weight of 138.9. 3 201004893 has a complex hexagonal structure at room temperature. The melting point is 921 〇c, the boiling point is 35 〇〇 ° C, and the density is 6.15 g/cm 3 '. In the air, the surface is oxidized and gradually dissolved in water. Soluble in hot water and acid. Although not ductile, it is slightly malleable. The resistivity is 5.70x10-6 〇0111. It burns at 445 < t or more and becomes oxide (La203) (refer to the chemistry dictionary). The rare earth element is generally stable to compounds having an oxidation number of 3, and is also trivalent. Recently, ruthenium has been researched and developed as an electronic material such as a metal gate electrode material or a high dielectric constant material (High-k), and thus it has been attracting attention. For steel metals, there is a problem that oxidation tends to occur during purification, and thus it is difficult to obtain a highly purified material without the presence of a high-purity product. Further, when the metal is placed in the air Φ djt .. . ^, it will oxidize in a short time and become black', so that it is difficult to handle. On the other hand, as a gate insulating film in a next-generation MOSFET, it is required to be thinned for use as a gate insulating film. 〗 〖The leakage current caused by the tunneling effect increases, making it difficult to operate normally. Because of the second alternative material, a high dielectric constant, high thermal stability, and a high energy barrier between electrons and electrons in the sputum are proposed (7)2.

Zr02, Α12〇3, La2〇3 〇 丨 丨 θ 于 于 于 于 于 La La La La La La La La La La La La La La La La La La La La La La La La La La La La La La La La La La La La La La La La La As the next generation and non-patent literature 3). However, in the report (refer to the non-patent document 1 film, and not related to the " element two literature, the object of the study is the characteristics and behavior of a7L. Therefore, it can be said that steel (oxidation) is still under study. At the stage, but 201004893, when investigating the complex oxygen characteristics of bismuth metal or cerium oxide or erbium and octagonal hexagram, if the ruthenium metal itself exists as a sputtering target, then the substrate The film formed on the enamel will become a cookware and a bamboo raft, so it can be tuned to the mutual interface between the yttrium and the yttrium, and the gamma J can be adjusted to form a bismuth compound. The characteristics of the insulating film, etc., have a greater advantage of increasing the degree of freedom of the left side. However, even if the sputtering target is made, the above-mentioned 'is also oxidized in a short time in the air. The problem. If an oxide film is formed on the upper surface, the electrical conductivity is lowered, resulting in poor ore reduction. χ If it is left in the air for a long time, (4) the moisture of the sputum towel will be covered by the white powder of the oxide, and it may even cause the problem of abnormal sputtering. Therefore, after the production, it is necessary to take an anti-oxidation countermeasure which is immediately vacuum-packed or covered with grease, but this is a rather complicated operation. Due to this problem, the target of bismuth elements cannot be put into practical use. There is also a proposal that m' is not used as a starting material, and 铭 acid mLaA1〇3) is used (see Non-Patent Document 2). In this document, it is described that the bismuth sulphate is more excellent than the Hf 〇 2 and Hf SiO of the high-k insulating film proposed as the next-generation m 〇 sfet. In this case, the process of film formation becomes a problem. According to this document, it is described that a film-forming film formed at a temperature-forming film (700 ° C) has a smaller leakage current than room temperature, and the inner valley is explained by the fact that film formation at a high temperature causes the defects in the film to disappear and the removal of LaAl is present.残3 residual oxygen. In this document, although the film forming process is not clearly described, it is expected that the formation of a high-Ug film by using a reactive gas due to high temperature (7 〇〇β(:) 5 201004893 film formation description] The film forming process is a high temperature ', ', and the problem is not solved. The month ''there' also has the proposal to use La2Hf2〇7 as a gate dielectric material (refer to the patent document... the implementation of this patent... In the example, the following method is used: by W delete 4 and H2 〇 as a chemical precursor layer stacking method or electron beam telecrystal method to grow on a wafer. In this case, the film forming method also becomes a problem. HfCU and ho are atomic layer deposition methods or electron beam epitaxy methods for chemical precursors, and it is difficult to control film formation, and the efficiency is also poor. If this method is sufficiently performed, there is a problem that fine deposition cannot be performed on the substrate. The film forming method of the plating method is a simple method, and has the advantages of high film formation speed and easy control, but the research on the use of base metal or cerium oxide or composite oxide of cerium and other elements as a sputtering target is still not Full enough to be effective Non-Patent Document 1: Non-Patent Document 1: Deco Wingsuke and other two people, "Research on Oxide Materials for High_k Gate Insulation Films", Electronic Society of Electrical Materials Research Society, Vol.6-13 ' Page.37-41 , September 21, 2001 Issued Non-Patent Document 2: Two other people, including Tochigi Masahiro, wrote "Aluminum sulphate Direct Bonding Gate Insulation Film" ' Toshiba review, Vol.62, No. 2 (2007) 37~41 Page Non-Patent Document 3: ALSHAREEF HN, QUEVEDO-LOPEZ M., WEN HC, HARRIS R., KIRSCH P., MAJHI P., LEE BH'JAMMY R" "Work function engineering using 201004893 lanthanum oxide interfacial layers" Appl. Phys.Lett·, Vol.89

No. 23 Page 232103-23 2103-3, (2006) Patent Document 1: Japanese Patent Laid-Open Publication No. 2007-324593 SUMMARY OF INVENTION PROBLEM TO BE SOLVED BY THE INVENTION As described above, metal ruthenium and oxygen rapidly combine to collapse The solution, in addition to the combination of cerium oxide and water to form a hydroxide into a powder, is difficult to maintain for a long time, even if it is made into a sputtering target, there is a problem that cannot be used in practice. In view of this, it is an object of the present invention to provide a stable La-containing oxide sintered body composed of oxides of lanthanum (La) and hafnium (Hf), particularly for high-k gate insulation. The film is formed with a La oxide-containing sputtering target. Means for Solving the Problems As disclosed in the above-mentioned problems, metal ruthenium is easily combined with oxygen, and yttrium oxide is combined with water to form argon oxide, so that it is difficult to store both for a long time. The invention of the present application is a method of adding cerium oxide to cerium oxide to form a sintered body, and further processing the sintered body into a dry form for use in ore-forming a film. The composition of the body and the body of the leather contains new substances. According to the above, the present invention provides: 1) An oxide sintered body which is composed of a composite oxide of steel and niobium, which is characterized in that the content of the sintered body is more than that of steel. It is characterized in that the oxide 1.2) is characterized in that the oxide 2) has a molar ratio of La:Hf in the oxide sintered body of the above 1): (1 3) oxide sintering as in the above 1) The oxide sintered body of any one of the above-mentioned items i) to 3) is characterized in that the relative density is 98. % or more, the maximum particle diameter is 50 or less, and the average particle diameter is 5 < m or more, 20 or less. 5) The oxide sintered body of any one of the above 1) to 4) is characterized by: The metal is 4 〇ppm or less, except for ☆, the transition metal ite is below 1G()ppm, which is below iGppm, ^, U is below 5 ppb. 6) A sputtering target, which is based on i 1) i (5) The oxide sintered body of any one of the present invention is used for the formation of an open insulating medium for a semiconductor element and the oxide sintered body of the above 5) Constitution. Further, the present invention provides: 8) a method for producing a sintered body of a sinter and an oxide, which is characterized in that La2(C〇3)3 powder and stimulating powder are used as raw material powders to form a molar composition of La and La. After mixing and mixing in a ratio of 1 to 1 2, the mixed powder is heated and synthesized in the atmosphere, and the synthetic powder is heated after being prepared into a powder by artificially cutting the synthetic material. Pressed to produce a sintered body 9) as above & 8) <Manufacturing side of oxide sintered body & Features J: La: Hf molar ratio is! :(丨〇1~丨)) (6) - A method for producing an oxide sintered body of cerium and lanthanum, (4)

</ br><br><br><br><br><br><br><br><br><br><br><br><br><br><br><br><br><br><br><br><br><br><br><br><br><br><br><br><br><br><br><br><br><br><br>< + A good side of the powder, with a _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ In the method of producing an oxide sintered body according to any one of the above 8) to 11), characterized in that the molar ratio of La:Hf is 1: (1.01 to 1.1). And a method for producing an oxide sintered body according to any one of the above 8) to 12), which is characterized in that it is 13 〇〇 15 15 〇 ( Rc, heating in a vacuum ^ 5 5 hours to carry out hot pressing of the synthetic powder 14) A method for producing an oxide sintered body, characterized in that the above-mentioned crucible is produced by the production method according to any one of the above 8) to 13) ) to 7) an oxide sintered body B) - an oxide sintered body sputtering target system A method, a system using the above manufacturing method of 14. EFFECTS OF THE INVENTION If the previous yttrium oxide sputtering target is placed in the air for a long time, the mussel 1J steel reacts with the moisture in the air to be covered with the white powder of the hydroxide, thereby causing the failure to proceed. The problem of normal clock reduction. The target consisting of the oxide and the oxide of the present invention can greatly delay the long-term storage of the problem during the period in which the problem is not practically produced. In addition, in general, steel is used to make the oxidized material of the sinter material of the (4) material. Therefore, it is particularly excellent as a interlayer insulating film. If it is a composition of a stoichiometric composition, La2Hf2〇7' is usually not It is more stable with 9 201004893 moisture reaction. However, m ’ sometimes has a partial La excess area due to subtle changes in composition. In this case, "the local oxidation or oxidation is exacerbated. There is a problem that the function as a sintered body or a target is greatly reduced. However, as in the invention of the present application, by the composition of the stoichiometric composition: the ratio is equal, or Compared with the ratio, the amount is slightly excessive. #Η卜 does not produce yttrium oxide...buts the reaction with water. Thereby, it has a remarkable effect of holding the function as a sintered body or a target for a long time. When the composition of the component (4) is equal, the mixture of the components and the soldering of the components are sufficiently segregated, thereby suppressing the formation of the local La oxide or the hydroxide. [Embodiment] The oxide sintered body of the present invention Or Qian Zhugan, which is made of steel ((4) is a compound of Lang's oxide, which is characterized in that the content of the sintered body or the target is more than or equal to the equivalent of yttrium. The ratio of La:Hf, that is, La: along: (i 〇 1.2), preferably La: Hf = 1: (ίο!, !)). The chemistry of lanthanum (La) and the oxide of (Hf) The metering composition is as described above for La2Hf2〇7. According to the group Be seen,

Hf surplus area. That is, Lm. = composition ratio of P 30 Hf- 1 . x ( l. OSxS 1.2). If x = ’, the durability of moisture is significantly worse, so the lower limit of x must

The δ needs to be 1·〇. Moreover, even A J , when the right X is greater than 丨·2, the characteristic is close to Hf〇2, so

In combination with the Hlgh-k material, it is considered that the characteristics are not improved, so the upper limit of X is set to h2. Further recommended conditions are \(10) called". When the oxide sintered body is not produced, it is preferred to use La2(c〇3)3 powder 201004893 L or ι^〇3 powder and Hf〇2 powder as raw material powder. Then, the method of setting the molar ratio of La to U to 1-2 is preferably carried out in such a manner that the financial and Hf molar ratios are set to 1_01 to 1.1. Ο The raw material powder of the above-mentioned La is not limited to the above-mentioned raw material powder by the heat treatment. The metal ruthenium may be used as the raw material for the production of barium hydroxide, cerium nitrate and cerium chloride. In addition, it is also possible to use a metal crucible for Hf. After mixing, it is heated and synthesized in an atmosphere of an oxygen-cut atmosphere, and then the synthetic material is pulverized to form a powder, and the synthetic powder is hot-pressed. The mixture is formed into a sintered body by a wet ball mill, and the production conditions are recommended to be 1350 to 155 (TC, heating for 5 to 25 hours) in the atmosphere. Further, ^(^~^(^.(: The hot pressing for i to 5 hours may be a recommended manufacturing condition as a sintering condition. The above conditions are effective for synthesis and sintering. Therefore, it should be understood that other conditions and other conditions may be employed. The mixing, synthesis and sintering 'segregation without La composition is the condition for obtaining a uniform structure, thereby obtaining a dense sintered body and a surplus of La oxide or La hydroxide. In this case, the sintered body or the target is disintegrated, and the life of the product is greatly shortened. In this case, 'by making the amount of Hf slightly more than the stoichiometric composition ratio of La2Hf207, even if there is such a component The variation (segregation) can also avoid the disintegration of the sintered body or the target. The reason is that by the excessive presence of Hf, even if the local composition changes, the occurrence of excessive segregation of La is suppressed, so that 11 201004893 is a stable LaHf oxide which remains in the sintered body or target. The addition of Hf which is slightly more than the stoichiometric composition ratio is a preferred condition for producing a stable sintered body filament. An oxide sintered body having a density of 9 or more and a maximum particle diameter of 50 or less and a sputtering target obtained by further processing the oxide sintered body. The increase in density and the generation of fine particles of the crystal grain size, and Good conditions for uniform film formation. n 戈 Previous, even if there is a literature on the use of La metal, La oxide or &amp; and other elements of the composite oxide film However, all of the documents are completed by gas phase reaction for atomic layer deposition method or electron beam epitaxy method in which HfCU and HA are used as chemical precursors, and the proposal as a sintered body or a sputtering target does not exist at all. The reason for this is considered to be that in the manufacturing step of a sintered body or a target composed of a La metal, a La oxide, or a composite oxide of U and other elements,

The La metal, the La oxide, or the composite oxide of La and other elements rapidly disintegrate and thus cannot maintain the shape. However, in the invention of the present application, it has been found that by the addition of Hf and the adjustment of the component 、, and further controlling the mixing, synthesis, and sintering conditions of the raw material powder, it is possible to suppress the disintegration of the La-containing composite oxide sintered body filament, thereby (iv) Use. Further, as described above, the addition of Hf is advantageous even as a material for (4). In general, rare earth elements containing antimony contain, in addition to lanthanum (La), Sc, Y, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, H〇, Er, Tm, Y. ^Lu, but because of the similar characteristics, it is difficult to separate from 12 in 2010. In particular, La is approximated, so the decrease in Ce content is not easy. However, since the rare earth element is similar in nature, there is no particular problem if the total amount of rare earth elements is less than 〇 ppm wtppm. Therefore, in the invention of the present application, it is preferable to contain a rare earth element having such a degree. However, in order to exhibit the characteristics as a thermal insulating film between La, it is preferred to reduce the content of the rare earth element. Further, in addition to this, there are impurities which are inevitably mixed. Analysis f is shown in Table 1. Although it contains a large amount of Zr (1600 wtppm), the fortunately, the invention of the present application deliberately adds Hf, and since Zr and Hf are very close to each other, even if Zr impurities are present, there is no problem. However, in order to exert the characteristics of Hf, it is a preferable condition to further reduce the impurity content. In summary, the invention of the present application contains the above substances. 13 201004893 [Table i] Impurity analysis results (, as early as: wt ppm)

Li 0.81 Be &lt;0.01 B 2.1 0 Matrix F 2.5 Na 15 Mg 0.81 A1 20 Si 17 P 0.72 S 1.6 Cl 5.7 K 3.9 Ca 4.8 Sc 0.61 Ti 2.6 V 0.11 Cr 5 Mn 0.3 Plant

Cd &lt;1 In Binder Sn 0.93 Sb &lt;0.5 Te &lt;5 I &lt;1 Cs &lt;5 Ba &lt;1 La Matrix Ce 415 Pr 110 Nd 155 Sm 2.1 Eu 0.06 Gd 3.1 Tb 0.25 〇y 2.5 Ho 1.5 Er &lt;0.05

Tm 0.39 Yb 0.57 Lu 0.59 Hf Matrix Ta Source W 15 Re &lt;0.1 Os &lt; 0.05 It &lt;0.1 Pt &lt;1 Au &lt;1 Hg &lt;0.5 Tl &lt; 0.1 Pb &lt;1 Bi &lt; 0.1 Th &lt ;0.005 U &lt;0.005

C 18 H 5.8 exists as a gas component, c is a harmful component that can be fixed, and in addition to the gas, there are different numbers of the gas. Although the gas component is sometimes used as a single-majority compound (C0, C) 〇2 and s exist in the form of a compound which is a constituent element. Since the gas component element is small in atomic weight and atomic radius, if it is not contained in a large amount, it exists as an impurity, and the properties of the material are not brought about. The purity of the steel of the invention of the present application is more preferably 3U or more except for the rare earth and therefore the composition of the gas 14 201004893. Further, it is preferable to: the metal contained in the sintered body 4 〇ppm or less 'The transition metal element other than Zr is 1 〇〇 ppm or less, pb is 5 ppm or less, and u and Th are 5 ppb or less. Since these will lower the characteristics of the semiconductor material, In particular, the alkali metal is easily moved in the gate insulating film to degrade the MOS interface characteristics, and the damage caused by the alpha ray emitted by the radioactive element may affect the operational reliability of the M〇s element. Further, transition metal elements such as Fe and Ni and heavy metal elements may cause failure in the interface joint portion. Further, according to the above manufacturing conditions, the relative density of the oxide sintered body can be set to 98% or more. 'The maximum particle size is 5 〇&quot; The average particle diameter below the nail is set to 5 / zm or more and 20 &quot; m or less. Thereby, generation of fine particles at the time of sputtering can be prevented, and a film excellent in uniformity can be formed.

A gate insulating germanium is formed by sputtering using the above target, and the gate insulating film is composed of La2Hf (2.24) 〇7 (u: the ratio of money is 丄: (1.0 to 1.2)) Preferably, it is an oxide of lanthanum and lanthanum of La2Hf(2〇2 2 2) 〇7 (La: then a ratio of 1 (1,01~丨.1)) (hereinafter referred to as "basic formation = La2Hf2" 7".) The constituents. The composition of the dry ingredients is directly reflected in the film formation. Further, in this way, the formation of the 镧 and the 铨鏠 & amp 〜 〜 吧 吧 吧 吧 吧 吧 吧 吧 吧 : : : : : : : : : : : : : : : : : : 该 该 该 该 该 该 该 该 该 该 该The processing system further fixes the free oxygen in the storage state, so it can be understood as an unnecessary condition. Especially in the next generation 15 201004893 MOSFET, etc. The heat treatment in the condition of the system is not necessary in the manufacturing conditions for avoiding heating. The embodiment will be described hereinafter. The embodiment is described in order to make the invention easy to understand and not to the present invention. Other embodiments and modifications within the scope of the technical idea of the present invention are included in the present invention. χ (Example 1) La La2(C〇3)3 powder and Hf〇2 powder are used as The molar ratio of the raw material Hf is : : 1 〇 3 Xing 3] is prepared by a wet ball mill 'two Γ. The powder is synthesized by heating in the atmosphere at 145 rc for 20 hours. Further, the synthesis is carried out by a ball mill. The material is carried out... U a pass group It is made into La2Hf2.044〇7 into the end of the...5〇〇°C. The synthetic powder is pressed by heat for 2 hours to make kgW. Ruler...9 and hot “ _ ❹ By this, the composition of the composition is La, Hf r\ « , 2.44 〇7 oxide sintered body: It is made by mechanical processing (10). The dry size after machining is X 6 mm, and the relative density of dry is 997 g/cm: theoretical density It is 7 954 g/cm3). Further, the coarse joint is bonded to the Μ 叉 待 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 The results of tissue observation. In Figure 2, Figure 2 shows the target, and the A chart does not randomly extract the 4 positions from the surface of the target, and the result of the visit is performed on the part. As shown in Figure 2,可 16 201004893 It is true that the average particle size is the heart, the minimum particle size is 6 5....'The maximum particle size is 35· A high-density sound of about 〇%: wide 'cell area ratio...) The results of the water immersion test were carried out on the remaining material of the La2Hf2.G4407 sintered body, which was made of the oxide on the layer of Fig. 3, and the composition of the composition was in the form of @2. The right is the result after 24 hours of water immersion test. As shown in Figure 3, ie, ## 氧化 氧化 氧化 氧化 氧化 氧化 氧化 氧化 氧化 氧化 氧化 氧化 氧化 氧化 氧化 氧化 氧化 氧化 氧化 氧化 氧化 氧化 氧化 氧化 氧化 氧化 氧化 氧化 氧化 氧化 氧化 氧化 氧化 氧化 氧化Oxidized steel) can quickly cause rot caused by oxidation or oxidation even when placed in the atmosphere, and it can be observed that it is white and then black. But on the La2Hf2 〇 "〇7 oxide sintered body Observed the rot. Further, in order to evaluate this, the intensity of the remaining material 20 after the water immersion test and the water immersion test for 24 hours (CPS, cycle per second, per week) was measured by x-ray diffraction (xd, X-ray diffraction). number). The results are shown in Figure 4. As shown in Fig. 4, there was no change in the remaining material after the water immersion test and 24 hours after the water immersion test. Thereby, it was confirmed that corrosion due to oxidation or oxidation did not occur. Further, a film of an oxide of La2Hf2.〇4407 was formed on the Si substrate by high-frequency sputtering using the target. As a result, the Si oxide film layer was not observed at the interface between the film of Si and the oxide of La2Hf2.44〇7. This means that the sputtering target can be used as a material for the gate insulating film. Further, in Example 1, La2(C〇3)3 powder was used as the raw material powder, but the same result was obtained even when the La2〇3 powder was used. There is no particular problem in selecting a raw material powder containing La 17 201004893. (Examples 2 to 8) La2(C〇3)3 powder and Hf〇2 powder were used as raw material powders with respect to the molar ratio of L Hf . For i, and Hf is Mm 1.〇4, (10), U6, UU u, respectively, the mixing is performed by a full ball mill. The manufacturing conditions were the same as in the first embodiment. The results were the same as those in Example 1. Inch

As long as the minimum molar ratio of Hf to La is maintained above ι〇, the rot is not particularly generated. If the molar ratio of Hf exceeds Μ, the characteristics of the gate insulating film as La are lowered. The upper limit of the molar ratio of the tendency Hf is set to 1.2. If the industrial use is required to be placed in the air for a long time, it will be covered by the white powder of the hydroxide after reacting with the moisture in the air. This causes a problem that normal sputtering cannot be performed, but the sintered body and the dry body composed of the steel and the oxide of the present invention do not cause such a problem. Further, by synthesizing the composition of the stoichiometric composition with La2Hf2〇7 or by the amount of the chemical-decade component #Hf, it has the following remarkable effect: the composite oxide of yttrium and yttrium is fixed by the strong oxidizing power Hf The free oxygen or residual oxygen contained in the solution prevents the free oxygen from moving in the film of the sputtered film of La2HG〇7, thereby reacting with the interface of Si to form harmful Si〇2. Therefore, the film is formed by using the dry film, and in addition to forming a uniform film, the above-mentioned remarkable effect is also achieved, and the formed film, in particular, as an electronic device disposed close to the 矽 base 18 201004893 plate, does not reduce or disturb the electronic device. Function, useful as a material grade for open-circuit insulation film. [Simplified description of the drawing] The appearance of the target formed by the sinter sintered body of the sinter oxide (1). The _ is not the oxide of La2Hf(2 Q44)07. Micrograph of the result of the observation of the structure of the sintered body. Fig. 3 is an external view (photograph) showing the result of the water immersion test of the remaining material of the oxide sintered body. Fig. 4 shows the diffraction by X-ray (xrd) A graph showing the results of measurement of the strength (CPS) of the remaining material of the sintered body of U2Hf(2 044)〇7 before the water immersion test and the water immersion test for 24 hours. [Explanation of main component symbols]

Claims (1)

201004893 VII. Patent application scope: 1. An oxide sintered body composed of a composite oxide of cerium and lanthanum, characterized in that the content of cerium contained in the sintered body is more than or equal to 镧. 2. The oxide sintered body of claim 1, wherein the molar ratio of La:Hf in the oxide is 1: (1.0 to 1.2). 3. The molar ratio of La:Hf in the oxide sintered body of the application of the scope of the patent application is i: (1 〇1~i 〇4. In the scope of application patent item! to item 3) The oxide sintered body of any of the items has a relative density of 98% or more, and the maximum particle diameter of 50 ^ or less has an average particle diameter of 5 &quot;m or more and 20 or less. 2. Please apply the scope of the patent range from item 4 to item 4 An oxygen-containing body in which the metal contained in the sintered body is 4 Λ scared to 3 hours later, the metal is 40 ppm or less, and the metal element other than the heart is 100 ppm or less, and is less than 1 〇 ppm, and is less than UT ppb.溅 6. A sputtering target comprising the oxide sintered body of any one of claims 1 to 5. τ 7· An ore-reducing dry, which is used for a semiconductor element The opening of the closed-electrode insulating film is formed by the oxide sintered body of the fifth application of the patent application. 8. The manufacturing method of the sintered body of the cerium and lanthanum oxide is as follows: using WC-terminal and service 2 powder As a raw material powder, it is mixed and mixed with a molar ratio of 1 to U, and then heated and synthesized in the atmosphere. The mixed powder is obtained by secondly pulverizing the synthetic material: 20 201004893 Finally, the synthetic powder is subjected to heat transfer to form a sintered body. 9. The method of the eighth aspect of the patent, wherein the emulsion sintered body is manufactured The molar ratio of the square La:Hf is 1: (1.01 to K1). 1〇. A method for producing a steel and an oxide sintered body, 1 characterized by using La2〇3 powder and 2 powder as raw materials ^ La After the composition of the molar ratio is 1~丨·2, the mixture is mixed and mixed: I gas is heated and synthesized to synthesize the mixed powder, and the outsider is convenient for the gift of the priest, (4) w W pulverized synthetic material to make the powder. In the cold, the synthetic powder is hot-pressed to obtain a sintered body. The second embodiment of the oxide sintered body of claim 10 wherein the molar ratio of La:Hf is 1: (1.0NU). For example, in the manufacturing method of the sintered body in the eighth to the "parts of the patent application, the oxide ❹ of the towel is mixed by a wet ball mill, and is heated at 135 〇 to 155 〇 C in the atmosphere, and heated at 5 to 25 Synthesize in hours. 13·If you apply for the scope of patents, item 8 The method for producing a sintered body according to the item 12, wherein the compound of J is heated at 1300 to 1500 〇c in a vacuum, and the method for producing a sintered body of the oxide is formed. The invention is characterized in that: one of the first to seventh items of the patent application scope of the manufacture of any one of the eighth to the third paragraphs of the patent application scope. The emulsion sintering of the item 21 201004893 A method for producing an oxide sintered body sputtering target, which comprises the method for producing an oxide sintered body according to claim 14 of the patent application. Eight, schema: (such as the next page) twenty two